This invention relates to polyethers having pendant hydroxyl moieties. More particularly, this invention relates to hydroxy-functionalized polyetheramines or polyhydroxyaminoethers (PHAE).
Hydroxy-functionalized polyetheramines are known and are described, for example, in U.S. Pat. Nos. 5,275,853 and 5,464,924. These polyetheramines exhibit oxygen transmission rates of from 0.57 to 19 cm3-mil/100 in2-atm (O2)-day, and are useful in the fabrication of barrier containers and films and as molding, extrusion and casting resins.
Hydroxy-functionalized polyetheramines can sometimes undergo cross-linking when fabricated at elevated temperatures. Modified, melt-stable polyetheramines, along with a process for their preparation, would clearly be desirable.
The present invention is, in a first aspect, a composition comprising a blend of an inorganic base, an organic base, a monofunctional organic nucleophile or a multifunctional organic nucleophile and a thermoplastic hydroxy-functionalized polyetheramine having the formula: 
wherein each A is independently an amine moiety and each B is independently a divalent aromatic moiety; R1 is hydrogen or a hydrocarbyl moiety; each X is independently a monovalent moiety; and n is a whole number from about 5 to about 1000.
In a second aspect, the present invention is a process for preparing a blend which comprises contacting an inorganic base, an organic base, a monofunctional organic nucleophile or a multifunctional organic nucleophile with a polyetheramine.
In a third aspect, the present invention is a laminate structure comprising one or more layers of an organic polymer and one or more layers of the composition of the first aspect.
In a fourth aspect, the present invention is an article fabricated from the composition of the first aspect or laminate structure thereof, and can be in the form of a molded or coextruded container, or an impermeable monolayer or multilayer film. The article is suitable for packaging oxygen-sensitive materials such as foodstuffs and medicines.
In a fifth aspect, the present invention is a solvent or waterborne coating prepared from the composition of the first aspect.
These hydroxy-functionalized polyetheramine blends are melt-stable thermoplastics and exhibit oxygen transmission rates below 5.0 cc-mil/100 in2-atm-day.
In addition to their use as barrier containers, films, laminate structures and coatings, the compositions of this invention are also useful as molding, extrusion and casting resins.
In preferred embodiments of the present invention, each A in the above formula is independently an amine moiety represented by any one of the formulas: 
wherein R is independently a hydrocarbyl, heterohydrocarbyl, inertly-substituted hydrocarbyl or inertly-substituted heterohydrocarbyl moiety, wherein the substituent(s) is hydroxyl, cyano, halo, arlyloxy, alkylamido, arylamido, alkylcarbonyl, or arylcarbonyl; R3 and R4 are independently a hydrocarbylene, heterohydrocarbylene, inertly-substituted hydrocarbylene or inertly-substituted heterohydrocarbylene moiety, wherein the substituent(s) is hydroxyl, cyano, halo, arlyloxy, alkylamido, arylamido, alkylcarbonyl, or arylcarbonyl with ethylene and p-xylylene being most preferred; each X is independently hydrogen, a primary, secondary or tertiary amino moiety, a hydroxyl moiety, an alkyl, heteroalkyl, inertly-substituted alkyl or inertly-substituted heteroalkyl group, an aryl or inertly-substituted aryl group, an alkoxy or inertly-substituted alkoxy group; an aryloxy or inertly-substituted aryloxy group, an alkanethio or inertly-substituted alkanethio group; an arenethio or inertly-substituted arenethio group, wherein the substituent(s) is hydroxyl, cyano, halo, arlyloxy, alkylamido, arylamido, alkylcarbonyl, or arylcarbonyl; or is represented by any one of the formulas: 
wherein R5 is independently an alkyl or heteroalkyl, inertly-substituted alkyl or heteroalkyl, aryl or inertly-substituted aryl group, wherein the substituent(s) is cyano, halo, arlyloxy, alkylamido, arylamido, alkylcarbonyl, or arylcarbonyl; R6 is independently hydrogen, an alkyl or heteroalkyl, inertly-substituted alkyl or heteroalkyl, aryl or inertly-substituted aryl group, wherein the substituent(s) is the same as that for R5; and R7 is an alkylene or heteroalkylene, inertly-substituted alkylene or heteroalkylene, arylene or inertly-substituted arylene moiety, wherein the substituent(s) is the same as that for R3 and R4.
In the more preferred embodiments of the present invention, X is 2-hydroxyethylamino, dimethylamino, diethylamino, piperadino, N-(2-hydroxyethyl)piperazino, methoxy, ethoxy, propoxy, 2-(methoxy)ethoxy, 2-(ethoxy)ethoxy, benzyloxy, phenyloxy, p-methylphenyloxy, p-methoxyphenoxy, 4-tert-butylphenyloxy, methylmercapto, ethylmercapto, propylmercapto, 2-(methoxy)ethylmercapto, 2-(ethoxy)ethylmercapto, benzylmercapto, 2,3-dihydroxypropylmercapto, phenylmercapto, p-methylphenylmercapto, acetate, benzoate, acetamido or benzenesulfonamido; R1 is hydrogen or methyl; R2 is methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 2,3-dihydroxypropyl, 2-(acetamido)ethyl, benzyl, phenyl, p-methoxyphenyl, p-methylphenyl; R3 is ethylene, 1,2-propylene or 1,2-butylene and R4 is ethylene, 1,2-propylene or 1,2-butylene, propylene, butylene, hexamethylene, 1,4-xylylene, 1,3-xylylene, 1,4-phenylene, 1,3-phenylene or 1,2-phenylene; and B is 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, methylenediphenylene, isopropylidenediphenylene, oxydiphenylene, thiodiphenylene, carbonyldiphenylene, diphenylflourene or a-methylstilbene or a combination thereof.
The hydroxy-functionalized polyetheramines employed in the present invention can be prepared by reacting a difunctional amine with a diglycidyl ether under conditions sufficient to cause the amine moieties to form a polymer backbone having amine linkages, ether linkages and pendant hydroxyl moieties. Residual epoxy end groups, should any remain, can optionally be reacted with a monofunctional nucleophile so that the isolated polyetheramine has no moieties capable of reacting with nucleophilic species.
As used herein, the term xe2x80x9cdiglycidyl etherxe2x80x9d means the reaction product of an aromatic, aliphatic or poly(alkylene oxide) diol with epichlorohydrin.
The difunctional amines which can be employed in the practice of the present invention include the bis-secondary amines and primary amines. Suitable bis-secondary amines include piperazine and substituted piperazines, e.g., dimethylpiperazine and 2-methylamidopiperazine; bis(N-methylamino)benzene, 1,2-bis(N-methylamino)ethane, and N,Nxe2x80x2-bis(2-hydroxyethyl)ethylenediamine. Preferred bis-secondary amines are piperazine, dimethylpiperazine, and 1,2-bis(N-methylamino)ethane. The most preferred bis-secondary amine is piperazine. Suitable primary amines include aniline and substituted anilines, e.g. 4-(methylamido)aniline, 4-methylaniline, 4-methoxyaniline, 4-tert-butylaniline, 3,4-dimethoxyaniline, 3,4-dimethyaniline; alkylamines, and substituted alkyl amines, e.g. butylamine and benzylamine; and alkanol amines; e.g. 2-aminoethanol and 1-aminopropan-2-ol. Preferred primary amines are aniline, 4-methoxyaniline, 4-tert-butylaniline, butylamine, and 2-aminoethanol. Most preferred primary amines are 4-methoxyaniline and 2-aminoethanol.
The diglycidyl ethers which can be employed in the practice of the present invention for preparing the polyetheramines include the diglycidyl ethers of the amide-containing bisphenols such as N,Nxe2x80x2-bis(hydroxyphenyl)-alkylenedicarboxamides, N,Nxe2x80x2-bis(hydroxyphenyl)arylene-dicarboxamides, bis(hydroxybenzamido)alkanes or bis(hydroxybenzamido)arenes, N-(hydroxyphenyl)hydroxybenzamides, 2,2-bis(hydroxyphenyl)acetamides, N,Nxe2x80x2-bis(3-hydroxyphenyl)glutaramide, N,Nxe2x80x2-bis(3-hydroxyphenyl)adipamide, 1,2-bis(4-hydroxybenzamido)ethane, 1,3-bis(4-hydroxybenzamide)benzene, N-(4-hydroxyphenyl)-4-hydroxybenzamide, and 2,2-bis(4-hydroxyphenyl)acetamide, 9,9-bis(4-hydroxyphenyl)fluorene, hydroquinone, resorcinol, 4,4xe2x80x2-sulfonyldiphenol, 4,4xe2x80x2-thiodiphenol, 4,4xe2x80x2-oxydiphenol, 4,4xe2x80x2-dihydroxybenzophenone, tetrabromoisopropylidenebisphenol, dihydroxy dinitrofluorenylidenediphenylene, 4,4-bis(4-hydroxyphenyl)methane, xcex1,xcex1-bis(4-hydroxyphenyl)ethylbenzene, 2,6-dihydroxynaphthalene and 4,4xe2x80x2-isopropylidene bisphenol (bisphenol A). More preferred diglycidyl ethers are the diglycidyl ethers of 9,9-bis(4-hydroxyphenyl)fluorene, hydroquinone, resorcinol, 4,4xe2x80x2-sulfonyldiphenol, 4,4xe2x80x2-thiodiphenol, 4,4xe2x80x2-oxydiphenol, 4,4xe2x80x2-dihydroxybenzophenone, tetrabromoisopropylidenebisphenol, dihydroxy dinitrofluorenylidenediphenylene, 4,4xe2x80x2-biphenol, 4,4xe2x80x2-dihydroxybiphenylene oxide, bis(4-hydroxyphenyl)methane, xcex1,xcex1-bis(4-hydroxyphenyl)ethylbenzene, 2,6-dihydroxynaphthalene and 4,4xe2x80x2-isopropylidene bisphenol (bisphenol A). Most preferred diglycidyl ethers are the diglycidyl ethers of 4,4xe2x80x2-isopropylidene bisphenol (bisphenol A), 4,4xe2x80x2-sulfonyldiphenol, 4,4xe2x80x2-oxydiphenol, 4,4xe2x80x2-dihydroxybenzophenone, and 9,9-bis(4-hydroxyphenyl)fluorene.
The inorganic bases which can be employed in the practice of the present invention include potassium hydroxide, sodium hydroxide, ammonium hydroxide, calcium oxide, magnesium oxide and mixtures thereof.
The organic bases which can be employed in the practice of the present invention include triethylenediamine and 1,5-diazabicyclo(5.4.0)undec-7-ene.
The monofunctional organic nucleophiles which can be employed in the practice of the present invention include a monofunctional amine, a hydroxyarene, an aryloxide salt, a carboxylic acid, a carboxylic acid salt, a thiol or a thiolate salt. Preferably, the monofunctional amine is dimethylamine, diethylamine, bis(2-hydroxyethyl)amine, dipohenylamine, piperadine, N-(2-hydroxyethylpiperadine); the hydroxyarene is phenol, cresol, methoxyphenol, or 4-tert-butylphenol; the aryloxide salt is sodium or potassium phenate; the carboxylic acid salt is sodium acetate, potassium acetate, calcium acetate, copper (II) acetate, sodium propionate, potassium propionate, calcium propionate, sodium benzoate, potassium benzoate, sodium ethylhexanoate, potassium ethylhexanoate, or calcium ethylhexanoate; the thiol is 3-mercapto-1,2-propanediol or benzenethiol; and the thiolate salt is sodium or potassium benzenethiolate.
The multifunctional organic nucleophiles which can be employed in the practice of the present invention include a multifunctional amine, a multifunctional carboxylic acid, a multifunctional carboxylic acid salt, a multifunctional phenol, a multifunctional phenate salt, a multifunctional thiol, a multifunctional thiolate salt, an amino acid or an amino acid salt. The preferred multifunctional organic nucleophiles are ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine, triethylenetetraamine, tetraethylenepentaamine, polyethyleneamine, citric acid, sodium or potassium citrate, glycine or sodium or potassium glycinate.
In general, the inorganic base, organic base, monofunctional organic nucleophile or multifunctional organic nucleophile is blended with the thermoplastic hydroxy-functionalized polyetheramines by conventional dry-blending methods using conventional means such as a barrel mixer, or a tumble mixer or by melt blending in an appropriate apparatus, such as a Banbury type internal mixer, rubber mill, single or twin screw extruder or compounder.
The inorganic base, organic base, monofunctional organic nucleophile or multifunctional organic nucleophile can also be co-dissolved with the thermoplastic hydroxy-functionalized polyetheramines in a suitable solvent and the solvent removed by evaporation. Examples of suitable solvents include 1-methyl-2-pyrrolidinone (NMP), and ethers or hydroxy ethers such as diglyme, triglyme, diethylene glycol ethyl ether, diethylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol phenyl ether, propylene glycol methyl ether and tripropylene glycol methyl ether.
Another suitable method of preparing the blends of the present invention comprises reacting a difunctional amine, a diglycidyl ether and optionally a monofunctional nucleophile and then blending the reaction product in situ with an inorganic base, an organic base or a mono- or multifunctional organic nucleophile in a solvent, in a molten state or in an extruder.
The amount of the inorganic base, organic base, monofunctional organic nucleophile or multifunctional organic nucleophile most advantageously blended with the hydroxy-functionalized polyether is dependent on a variety of factors including the specific polymers used in making the blends, as well as the desired properties of the products resulting from the blends. Typical amounts can range from about 0.1 to about 15 weight percent of the blend. Preferably, the inorganic base, organic base, monofunctional organic nucleophile or multifunctional organic nucleophile is used in an amount of from about 0.5 to about 10 weight percent, more preferably from about 0.5 to about 3.0 weight percent and, most preferably, from about 0.1 to about 2.0 weight percent of the blend.
Films prepared from the composition of the present invention generally have oxygen transmission rates (OTR) of from about 0.05 to about 1.0 cc/mil/100 in2/atm/day, at 25xc2x0 C. and 60 percent relative humidity (ASTM D-3985) and carbon dioxide transmission rates (CO2TR) of from about 0.5 to about 4.0 cc-mil/100 in2-atm-day, at 23xc2x0 C. and 0 percent relative humidity.
Films and laminate structures can be formed from the composition of the present invention by using conventional extrusion techniques such as feedblock extrusion, multimanifold die coextrusion or combinations of the two, or by solvent spraying or solution casting. Solution casting is a well known process and is described, for example, in the Plastics Engineering Handbook of the Society of the Plastics Industry, Inc., 4th Edition, page 448.
Containers and other molded parts can be fabricated from the films or laminate structures comprising the composition of the present invention by using conventional fabricating techniques for thermoplastic polymers such as compression molding, injection molding, extrusion, thermoforming, blow molding and solvent casting.
In general, laminate structures can be formed from the composition of the present invention by coextruding one or more layers of an organic polymer and one or more layers of the composition of the present invention, wherein the layer of the composition of the present invention is adhered to a contiguous organic polymer layer with or without an adhesive layer therebetween. Laminate structures also can be formed by co-injection of the composition of the present invention with an organic polymer; in some cases, preforms produced by such co-injection can be blow-molded into multilayer containers.
The laminate structure can be a three-layer laminate comprising a first outer layer of an organic polymer, a core layer of the composition of the present invention and a second outer layer of an organic polymer which is the same as or different from the organic polymer of the first outer layer.
The laminate structure can also be a three-layer laminate comprising a first outer layer of the composition of the present invention, a core layer of an organic polymer and a second outer layer of an organic polymer which is the same as or different from the organic polymer of the core layer.
The laminate structure can also be a three-layer laminate comprising a first outer layer of the composition of the present invention, a core layer of an organic polymer and a second outer layer of the composition of the present invention.
The laminate structure can of course comprise more than three layers, including, for example, five-layer structures comprising outer layers and an innerlayer of an organic polymer separated by two layers of the composition of the present invention.
Organic polymers which can be employed in the practice of the present invention for preparing the laminate structure include crystalline thermoplastic polyesters, such as polyethylene terephthalate (PET); polyamides, polyolefins, and polyolefins based on monovinyl aromatic monomers.
Polyesters and methods for their preparation are well known in the art and reference is made thereto for the purposes of this invention. For purposes of illustration and not limitation, reference is particularly made to pages 1-62 of Volume 12 of the Encyclopedia of Polymer Science and Engineering, 1988 revision, John Wiley and Sons.
Polyamides which can be employed in the practice of the present invention include the various grades of nylon, such as nylon-6, nylon-6,6 and nylon-12.
Polyolefins which can be employed in the practice of the present invention include, for example, low density polyethylene, linear low density polyethylene, very low density polyethylene, polypropylene, polybutene, ethylene/vinyl acetate copolymers, ethylene/propylene copolymers and ethylene/butene-1 copolymers.
Polyolefins based on monovinyl aromatic monomers which can be employed in the practice of the present invention include polystyrene, polymethylstyrene, styrene/methylstyrene or styrene/chlorostyrene copolymers.
Other organic polymers of the polyester or polyamide type can also be employed in the practice of the present invention for preparing the laminate structure. Such polymers include polyhexamethylene adipamide, polycaprolactone, polyhexamethylene sebacamide, polyethylene 2,6-naphthalate and polyethylene 1,5-naphthalate, polytetramethylene 1,2-dioxybenzoate and copolymers of ethylene terephthalate and ethylene isophthalate.
The thickness of each layer in the laminate structure is dependent on a number of factors, including the intended use, materials stored in the container, the length of storage prior to use and the specific composition employed in each layer of the laminate.
In general, the laminate structure will have a total thickness of from about 0.5 to about 500 mils, preferably from about 1.0 to about 250 mils; with the thickness of the hydroxy-functionalized polyetheramine layer(s) being from about 0.05 to about 100 mils, preferably from about 0.1 to about 50 mils; and the thickness of the polyester layer(s) being from about 0.45 to about 400 mils, preferably from about 0.9 to about 200 mils.
The composition of the present invention can also be prepared and fabricated into a shaped article by a reactive extrusion process wherein the reactants are fed into and reacted in an extruder using the conditions described in U.S. Pat. No. 4,612,156, which is incorporated herein by reference.
The following working examples are given to illustrate the invention and should not be construed as limiting its scope. Unless otherwise indicated, all parts and percentages are by weight.